Matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometric study of 2,3-dihydro-1,4-benzoxazepines

Fragmentations of the protonated adduct ions [M+H](+) of seven 1,4-benzoxazepine derivatives were studied using 'post-source decay' matrix-assisted laser desorption/ionization (PSD MALDI) and electrospray nozzle-skimmer collisionally induced dissociation (ESI-CID) mass spectrometric methods. It was found that both methods generated mainly product ions arising from the cross-ring cleavages of the benzoxazepine ring. Similar product ions were generated under MALDI and ESI conditions; however, it was observed that the loss of the alkylene unit from the N-substituted benzoxazepine, and the loss of a H(2)X molecule (where X = O or S), are more preferred under ESI conditions. Based on the experimental results a mechanism is also proposed for the fragmentation of the oxazepines studied.     

Impedance measurements for pressed-pellet electrode membranes based on silver iodide and silver iodide/silver sulfide with solution contacts

Impedance characteristics of pressed pelletm membranes based on silver iodide, mixed $\text{AgI}\text{Ag}{}^2\text{S}$ with molar ratios of 10:1, 1:1 and 1:10, and silver sulfide are investigated by using solution contacts and a computer-controlled automatic measuring system. As membrane bulk impedances were commensurable with those of contacting solutions, special regression methods were necessary for evaluation. Typical resistivities were, in the order indicated above, as follows: 14, 2, 0.3, 0.1 and 0.1 kΩ cm, respectively. Thus, mixing of silver sulfide into the silver iodide matrix decreases dramatically the membrane resistance. These measured bulk membrane resistances are not affected by changes in composition and concentration of bathing solutions, and even the low-frequencies parts of impedance plots were not influenced by different stirring conditions, even in presence of corroding solutions such as thiosulfate or cyanide. Sorption also had no manifest effect on the impedance characteristics, but increasing pressure during membrane preparation or heat treatment significantly increased membrane resistances.     

Identification and fragmentation study of plasticizers with post-source decay matrix-assisted laser desorption/ionization mass spectrometry

A detailed investigation of the most commonly used plasticizers, such as phthalate, adipate and trimellitate esters, using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and post-source decay (PSD) MALDI-TOFMS/MS is described. It is shown that PSD MALDI-TOFMS/MS is capable of unambiguous determination of the different types of plasticizers. The determination of the types of plasticizers from different PVC samples by PSD MALDI-TOFMS/MS, without the need for solvent extraction, is also demonstrated. The fragmentation mechanisms of these plasticizers cationized with protons and sodium ions are also reported.     

Homocoenzyme B12 and bishomocoenzyme B12: covalent structural mimics for homolyzed, enzyme-bound coenzyme B12

Efficient electrochemical syntheses of "homocoenzyme B(12)" (2, Co(beta)-(5'-deoxy-5'-adenosyl-methyl)-cob(III)alamin) and "bishomocoenzyme B(12)" (3, Co(beta)-[2-(5'-deoxy-5'-adenosyl)-ethyl]-cob(III)alamin) are reported here. These syntheses have provided crystalline samples of 2 and 3 in 94 and 77 % yield, respectively. In addition, in-depth investigations of the structures of 2 and 3 in solution were carried out and a high-resolution crystal structure of 2 was obtained. The two homologues of coenzyme B(12) (2 and 3) are suggested to function as covalent structural mimics of the hypothetical enzyme-bound "activated" (that is, "stretched" or even homolytically cleaved) states of the B(12) cofactor. From crude molecular models, the crucial distances from the corrin-bound cobalt center to the C5' atom of the (homo)adenosine moieties in 2 and 3 were estimated to be about 3.0 and 4.4 A, respectively. These values are roughly the same as those found in the two "activated" forms of coenzyme B(12) in the crystal structure of glutamate mutase. Indeed, in the crystal structure of 2, the cobalt center was observed to be at a distance of 2.99 A from the C5' atom of the homoadenosine moiety and the latter was found to be present in the unusual syn conformation. In solution, the organometallic moieties of 2 and 3 were shown to be rather flexible and to be considerably more dynamic than the equivalent group in coenzyme B(12). The homoadenosine moiety of 2 was indicated to occur in both the syn and the anti conformations.     

Convergence of Utility Indifference Prices to the Superreplication Price

A discrete-time financial market model is considered with a sequence of investors whose preferences are described by concave strictly increasing functions defined on the positive axis. Under suitable conditions, we show that the utility indifference prices of a bounded contingent claim converge to its superreplication price when the investors’ absolute risk-aversion tends to infinity.     

Evaluation of the inelastic mean free path (IMFP) of electrons in polyaniline and polyacetylene samples obtained from elastic peak electron spectroscopy (EPES)

The inelastic mean free path (IMFP) of electrons was determined experimentally for selected polyaniline and polyacetylene samples with Ag and Ni references using elastic peak electron spectroscopy (EPES). The surface composition was determined by XPS and density by helium pycnometry. The high resolution hemispherical ESA-31 and ADES-400 spectrometers were used for measurements in the energy range E = 0.5–3.0 keV and E =0.4 − 1.6 keV, respectively. The integrated elastic peak intensity ratios for sample and reference were calculated using the Monte Carlo (MC) algorithm based on the electron elastic scattering cross-sections database NIST SRD64 version 3.1 and applying TPP-2M IMFPs for polymers. Surface excitation parameters (SEP) and material parameters ( _ach ) for polymers were determined, using the model of Chen, from comparison of measured and MC calculated elastic peak intensity ratios. These corrections proved to be efficient in decreasing the percentage deviations between the obtained IMFPs and the TPP-2M formula IMFPs. The elastic peak of hydrogen was observed in the EPES spectra of polymers. The experimental contribution of the hydrogen to the total elastic peak was 0.58%, while this value obtained from the MC simulations was 1.98%.      

Sub-10-fs, terawatt-scale Ti:sapphire laser system

A three-stage, 1-kHz amplifier system delivering pulses shorter than 10 fs with a peak power in excess of 0.3 TW is reported. Passive and active spectral intensity and phase control allows the preservation of a bandwidth of 120 nm (FWHM) to as high as multimillijoule energy levels and temporal compression of the broadband pulses close to their Fourier limit. The system is scalable to peak powers well beyond 1 TW and holds promise for substantially advancing the state of the art of coherent laboratory soft-x-ray sources.     

Binding of some environmental pollutants to corn protein zein studied by high-performance liquid chromatography.

The strength and the character of the binding of 12 organic solvents to the corn protein zein was determined by preparing zein-coated carbon stationary phase and by measuring the retention of solvents on a high-performance liquid chromatographic column filled with this stationary phase. The relationship between the physicochemical parameters and binding characteristics of solvents was elucidated by principal component analysis. Various interactive forces are involved in the binding of solvent to the protein. The strength of the binding is dominantly influenced by the molecular hydrophobicity while the Gaussian or non-Gaussian distribution of the adsorption strength is markedly dependent on the polarity parameters of the solvent. Sterical correspondences exerted considerable influence on each binding parameter.